Dispersing agent

ABSTRACT

Poly(glutamic acid) is used as a dispersing, soil-suspending or anti-redeposition agent in laundry detergent or other cleaning compositions that also contain a detersive surfactant. Suitable polymers include not only the homopolymers of glutamic acid but also block, graft or random copolymers of glutamic acid with biodegradable monomers or polymers, e.g., other amino acids or polyethylene glycol.

FIELD OF THE INVENTION

The present invention relates to the use of polymers of glutamic acid asdispersing agents, especially in cleaning compositions, for example inlaundry detergent compositions.

BACKGROUND OF THE INVENTION

Polyacrylates and acrylate/maleate copolymers are widely used asdispersing agents, specifically as soil-suspending and/oranti-redeposition agents, in detergent compositions and confer importantcleaning benefits thereon. However, these polymers and copolymers arenot easily biodegradable, thereby posing potential environmentalproblems. Carboxymethyl cellulose is biodegradable at a degree ofsubstitution (DS) of less than 0.7 but, although it confers somewhiteness-maintenance benefit to detergent compositions, it is deficientwith regard to soil-suspension properties. Accordingly, there is a needin the art for effective agents that will undergo rapid andsubstantially complete biodegradation; furthermore, it would beadvantageous if such agents were to be derived from natural startingmaterials. EP-A-454126 discloses detergent formulations comprising from5% to 50% by weight of polyaminoacid derived from glutamic acid.(Published Oct. 30, 1991) .

SUMMARY OF INVENTION

The present invention relates to the use of dispersing agent, especiallyin a cleaning composition, of a polymer of glutamic acid, wherein thepolymer of glutamic acid is present at a level of from 0.1% to 4.95% byweight of the composition. In one aspect, the present invention providesa cleaning composition (a) from 0.1% to 4.95% by weight of a polymer ofglutamic acid and (b) a detersive surfactant, preferably selected fromnonionic, anionic, cationic, ampholytic and zwitterionci detersivesurfactants.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

The polymers suitable as component (a) may be derived from L-glumaticacid, D-glumatic acid or mixtures, e.g. racemates, of these L and Disomers. The L isomer and D, L racemate are currently preferred. Thepolymers suitable as component (a) in the present compositions includenot only the homopolymers of glutamic acid but also copolymers, such asblock, graft or random copolymers, containing glutamic acid. Thus,copolymers of glutamic acid with at least one other (preferablybiodegradable) monomer, oligomer or polymer come into consideration.These include, for example, copolymers containing at least one otheramino acid, such as aspartic acid, ethylene glycol, ethylene oxide, (oran oligimer or polymer of any of these) or polyvinyl alcohol.

Glutamic acid may, of course, carry one or more substituents and thepolymers useful as component (a) include those in which a proportion orall of the glutamic acid monomers are substituted. Substituents include,for example, alkyl, hydroxy alkyl, aryl and arylalkyl, commonly with upto 18 carbon atoms per group, or polyethylene glycol attached by esterlinkages.

The expression "poly (glutamic acid)" and cognate expressions herein areto be constructed as covering any of the aforesaid possibilities unlessthe context otherwise demands.

A homopolymer of glutamic acid may be prepared in a two-step process, inwhich (i) glutamic acid is treated with phosgene or an equivalentreagent, e.g. diphosgene, at a temperature of from 15° to 70° to form anN-carboxyanhydride (NCA), and (ii) ring-opening polymerisation of theN-carboxyanhydride is effected with a base to yield poly-(glutamicacid). Suitable bases include alkoxides, e.g. alkali metal alkoxidessuch as sodium mothoxide, organometallic compounds and primary,secondary or tertiary amines, for example butylamine or triethylamine.Such bases are readily available or easily synthesised by methods knownin the art, as are glumatic acid and (di) phosgene.

Although no representation as to the actual reaction mechanism is madeherein, the aforesaid synthesis may be illustrated by the followingreaction scheme: ##STR1##

It will be noted that the pathways lead, respectively, to an alpha (a)form of a gamma (r) from of the glutamic acid polymer. The presentinvention includes both forms and mixtures thereof. Furthermore,although the pendant carboxylate groups are shown in the acid form(--COOH), the invention also extends to polymers wherein some or all ofsuch groups are in a salt form, for instance a metal (e.g. sodium),ammonium or quaternary ammonium salt.

The aforesaid synthesis via the N-carboxyanhydride may be carried outunder conditions mild enough to ensure that the resultant polymerretains the stereochemistry of the starting material. Thus, for example,it is possible to obtain from L-glutamic acid a polymer that containsonly L-amino acid units.

The present invention is not, however, limited to polymers of glutamicacid that are made by the aforesaid synthesis route. Thus, for example,the bacterial production of poly (glumatic acid) also comes intoconsideration herein. Bacterial production of poly (glutamic acid) isdescribed, for example in EP-A-410, 638 (Takeda). Bacterial syntheticprocesses will commonly yield poly (L-glutamic acid) although bacteriaare known that will provide the D-form. Polymers of glutamic acid mayalso be prepared by thermal polycondensation of the nonomers: thisusually yields a polymer of the D, L racemate.

A block copolymer of glutamic acid and polyethylene glycol may beprepared by the ring-opening polymerisation of the N-carboxyanhydride ofglutamic acid using polyethylene glycol diamine (obtainable as"Jeffamine 4000") whilst preventing salt formation at the amine chainends by carrying out the reaction in the presence of a non-nucleophilicbase. In place of the said diamine, it is also possible to use, forexample, polyethylene glycol which has been treated to terminal alkoxidegroups.

The molecular weight of the glutamic acid polymers and copolymers willbe typically from 1000 to 100,000, e.g. 3,000 to 7,000 although neitherlower nor higher molecular weights are precluded herein. Molecularweights may be measured by gel permeation chromatography withdifferential iscometer detector. Illustrative reaction schemes for thepreparation of copolymers include the following: ##STR2##

The above example demonstrates how a random or, if the monomers wereadded sequentially, a diblock copolymer could be synthesised. Thesynthesis could be used with any anionically polymeriable monomer.##STR3##

The above demonstrates the copolymerisation of different amino acidsfrom their respective NCA's and copolymerisation with a base asinitiator. This too would give random or block copolymers depending uponhow the addition of the respective monomers was carried out. Also thisscheme are not limited to two monomers; more is possible. ##STR4##

The above demonstrates the possibility that poly(glutamic acid) (PGA)could be grafted onto a suitable polymeric backbone. Poly (vinvyalcohol) is used as the backbone which is manufactured via thehydrolysis of poly (vinyl-acetate), hence it can be considered as acopolymer with --OH and --OAc sidechains. However the level of --OAc canbe zero and is usually not more that 25%. This shows that a graft can becarried out on homopolymers or copolymers containing a suitable group(assuming that other groups in the copolymer do not interfere withpolymerisation).

The poly (glutamic acid) may be used as a dispersing agent (which termherein includes a clay-soil suspending agent and or an anti-redepositionagent) in both liquid detergent compositions and solid (e.g. granular orother particulate) detergent compositions and are employed therein at alevel from 0.1% to 4.95 percent, preferably 0.2 to 4.75 percent and morepreferably 1 to 4.25 percent, by weight of the compositions.

The detersive surfactant (b) will typically be used in an amount of from10 to 50 percent, preferably 1 to 30, more preferably 5 to 20 percent,by weight. Although the poly (glutamic acid) may be included in a widevariety of cleaning compositions, for example hard-surface and otherhousehold cleaners, dishwashing compositions and personal care productssuch as shampoos, soaps and toothpastes, the compositions of the presentinvention in certain preferred embodiments will be formulated as laundrydetergent compositions, e.g. general-purpose or heavy-duty, liquid orgranular laundry detergent compositions, that contain the poly (glumaticacid) dispersing agent and a detersive surfactant and, optionally, oneor more further components conventional in the art, for example adetergent builder, a bleach (in particular a source of hydrogenperoxide, e.g. sodium perbonate), a bleach activator an enzyme, apolymeric soil-release agent, a chelating agent, a conventionalclay-soil removal-anti-redeposition agent, a polymeric dispersing agent,a brightener, a suds suppresor, a pH-buffering agent, a dye or apigment.

It will be understood that any of the above mentioned components,whether essential or optional, may be constituted, if desired, by amixture of two or more compounds of the appropriate description.

Examples of various detersive surfactants suitable for use as component(b) in the present composition are mentioned in the followingdescription, which in turn is followed by examples of the variousoptional components that come into consideration for inclusion in thepresent compositions.

Nonionic Surfactants

The laundry detergent compositions of this invention may contain anonionic surfactant.

Suitable nonionic surfactants include the polyethylene oxide condensatesof alkly phenols, e.g., the condensation products of alkyl phenolshaving an alkyl group containing from 6 to 8 carbon atoms, in either astraight-chain or branched-chain configuration, with from 1 to 12 molesof ethylene oxide per mole of alkyl phenol.

Suitable nonionics also include the condensation products of aliphaticalcohols containing from 8 to 22, preferably 12 to 18, carbon atoms, ineither straight-chain or branched-configuration, with from 2 to 12,preferably 3 to 7, moles of ethylene oxide per mole of alcohol.

Suitable nonionic surfactants also include the fatty acyl or alkylcondensation products of carbohydrates and their derivatives such asglycosides, aminodeoxy forms, and polyols. Examples include coco-alkylpolyglucosides and tallow-acyl polyglycerides. The nonionic surfactantsmay typically be used in an amount from 0.5 to 20%, preferably from 3 to15% and more preferably from 5 to 10%, by weight of the totalcomposition.

Anionic Surfactants

The detergent compositions of the previous invention can contain, inaddition to the nonionic surfactant system of the present invention, oneor more anionic surfactants as described below.

Alkyl Ester Sulfonate Surfactant

Alkyl ester sulfonate surfactants hereof include linear esters of C₈-C₂₀ carboxylic acids (i.e. , fatty acids) which are sulfonated withgaseous SO₃ according to "The Journal of the American Oil ChemistsSociety", 52 (1975), pp 323-329. Suitable starting materials wouldinclude natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplication, comprise alkyl ester sulfonate surfactants of thestructural formula: ##STR5## wherein R³ is a C₈ -C₂₀ hydrocarbyl,preferably an alkyl, or combination thereof, R₄ is a C₁ -C₆ hydrocarbyl,preferably an alkyl, or combination thereof, and M is a cation whichforms a water soluble salt with alkl ester sulfonate. Suitablesalt-forming cations include metals such as sodium, potassium, andlithium, and substituted or unsubstituted ammonium cations, such asmonoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ isC₁₀ -C₁₆ alkyl and R⁴ is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R³ is C₁₀ -C₁₆ alkyl.

Alkyl Sulfonate Surfactant

Alkyl sulfate surfactants hereof are water soluble salts or acids of theformula ROSO₃ M wherein R preferably is a C₁₀ -C₂₄ hydrocarbyl,preferably an alkyl or hydroxyalkyl having a C₁₀ -C₂₀ alkyl component,more preferably a C₁₂ -C₁₈ alkyl or hydroxyalkyl, and M is H or acation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium),or ammonium or substituted ammonium (e.g., methyl-, dimethly-, andtrimethyl ammonium cations and quaternary ammonium cations such astetramethlyammonium and dimethyl piperdinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Alkyl chains 12-16 carbon atoms, more preferably 14-15 carbon atoms arepreferred.

Alkyl Alkoxylated Sulfate Surfactants

Alkyl alkoxylated sulfate surfactants hereof are water soluble salts oracids of the formula RO(A)_(m) SO₃ ^(M) wherein R is an unsubstitutedC₁₀ -C₂₄ alkyl or hydroxyalkyl group having a C₁₀ -C₂₄ alkyl component,preferably a C₁₂ -C₂₀ alkyl or hydroxyalkyl, more preferably an alkylgroup having from 12 to 18 carbon atoms, especially from 12 to 15 carbonatoms. A is an ethoxy or propoxy unit, m is greater than zero, typicallybetween about 0.5 and about 6, more preferably between 0.5 and about 3,and M is H or a cation which can be, for example, a metal cation (e.g.,sodium, potassium, lithium, calcium, magnesium, etc.), ammonium orsubstituted ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperdinium cations and those derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine,mixtures thereof, and the like. A preferred surfactant is C₁₂ -C₁₅ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₅ E(3.0)M). Other exemplarysurfactants include C₁₂ -C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂-C₁₈ E(1.0)MO, C₁₂ -C₁₈ alkyl polyethoxylate (2.25) sulfate (C₁₂ -C₁₈E(2.25)M), C₁₂ -C₁₈ alkyl polyethoxylate (3.0) sulfate (C₁₂ -C₁₈E(3.0)M), and C₁₂ -C₁₈ alkyl polyethoxylate (4.0) sulfate (C₁₂ -C₁₈E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Other Anionic Surfactants

Other anionic surfactants useful for detersive purposes can also beincluded-in the compositions hereof. These can include sales (including,for example, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of soap, C₉ -C₂₀ linearalkylbenzenesulphonates, C₈ -C₂₂ primary or secondary alkanesulphonates,C₈ -C₂₄ olefinsulphonates, sulphonated polycarboxylic acids prepared bysulphonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179, alkylglycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl tautares, fatty acid amides of methyl tauride,alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂ -C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆ -C₁₄ diesters),N-acyl sarcosinates, sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beingdescribed below), branched primary alkyl sulfates, alkyl polyethoxycarboxylates such as those of the formula RO(CH₂ CH₂ O)_(k) CH₂ COO--M⁺wherein R is a C₈ -C₂₂ alkyl, k is an integer from 0 to 10, and M is asoluble salt-forming cation, and fatty acids esterified with isethionicacid and neutralized with sodium hydroxide. Resin acids and hydrogenatedresin acids are also suitable, such as rosin, hydrogenated rosin, andresin acids and hydrogenated resin acids present in or derived from talloil. Further examples are given in "Surface Active Agents andDetergents" (Vol. I and II by Schwartz, Perry and Berch). A variety ofsuch surfactants are also generally disclosed in U.S. Pat. No.3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line58 through Column 29, line 23 (herein incorporated by reference).

Preffered anionic surfactants systems employed in the detergentcompositions of the invention are free of alkyl benzene sulfonate salts.A highly preferred system comprises a mixture of a major proportion of aC₁₄ -C₁₅ primary alkyl sulfate and a minor proportion of a C₁₂ -C₁₅alkyl ethoxysulfate containing an average of three ethoxy groups permole of alkyl ethoxy sulfate. The laundry detergent compositions of thepresent invention typically comprise from about 1% to about 20%,preferably from about 3% to about 15% and most preferably from 5% to 10%by weight of anionic surfactants.

Other Surfactants

The detergent compositions of the present invention may also containcationic, ampholytic, zwitterionic, and semi-polar surfactants.

Cationic detersive surfactants suitable for use in the detergentcompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyldimethylanium halogenides, and thosesurfactants having the formula:

    (R.sup.2 (OR.sup.3).sub.y)(R.sup.4 (OR.sup.3).sub.y).sub.2 R.sup.5 N+X.sup.-

wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl ringstructures formed by joining the two R⁴ groups, --CH₂ CHOH--CHOHCOR⁶CHOHCH₂ OH wherein R⁶ is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Other cationic surfactants useful herein are also described in the U.S.Pat. No. 4,228,044, Cambre, issued Oct. 14, 1980, incorporated herein byreference. When included therein, the detergent compositions of thepresent invention typically comprise from 0% to about 25%, preferablyfrom about 3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the detergentcompositions of the present invention. These surfactants can be broadlydescribed as aliphatic derivatives of secondary or tertiary amines, oraliphatic derivatives of heterocyclic secondary and tertiary amines inwhich the aliphatic radical can be straight chain or branched. One ofthe aliphatic substituents contains at least about 8 carbon atoms,typically from about 8 to about 18 carbon atoms, and at least onecontains an anionic water-solubilizing group, e.g., carboxy, sulfonate,sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30,1975 at column 19, lines 18-35 (herein incorporated by reference) forexamples of ampholytic surfactants.

When included thereit, the detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in detergentcompositions . These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48 (herein incorporated by reference) for examples ofzwitterionic surfactants. When included therein, the detergentcompositions of the present invention typically comprise from 0% toabout 15%, preferably from about 1% to about 10% by weight of suchzwittarionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of from about 10 to about18 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to about 18 carbon atoms and a moiety selected from thegroup consisting of alkyl and hydroxyalkyl moieties of from about 1 toabout 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula ##STR6## wherein R³ is an alkyl,hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing fromabout 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylenegroup containing from about 2 to about 3 carbon atoms or mixturesthereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkylgroup containing from about 1 to about 3 carbon atoms or a polyethyleneoxide group containing from about 1 to about 3 ethylene oxide groups.The R⁵ groups can be attached to each other, e.g., through an oxygen ornitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀ -C₁₈ alkyldimethyl amine oxides and C₈ -C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides.

When included therein, the detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such semi-polar nonionic surfactants.

Builders

The detergent compositions of the present invention can compriseinorganic or organic detergent builders to assist in mineral hardnesscontrol.

The level of the builder can vary widely depending upon the end use ofthe composition and its desired physical form. Liquid formulationstypically comprise at least 1%, more typically from about 5% to about50%, preferably about 5% to about 30%, by weight of detergent builder.Granular formulations typically comprise at least about 1%, moretypically from about 10% to about 80%, preferably from about 15% toabout 50% weight of the detergent builder. Lower or higher levels ofbuilder, however, are not meant to be excluded.

Inorganic detergent builders include, but are not limited to, the alkalimetal, ammonium and alkanolammonium salts of polyphosphates (exemplifiedby the tripolyphosphates, pyrophosphates, and glassy polymericmeta-phosphates), phosphonates, phytic acid, silicates, carbonates(including bicarbonates and sesquicarbonates), sulphates, andaluminosilicates. Borate builders, as well as builders containingborate-forming materials that can produce borate under detergent storageor wash conditions (hereinafter, collectively "borate builders"), canalso be used but are not preferred at wash conditions less than about50° C., especially less than about 40° C. Preferred builder systems arealso free of phosphates. Examples of silicate builders are the alkalimetal silicates, particularly those having a SiO₂ :Na₂ O ratio in therange 1.6:1 to 3.2:1 and layered silicates, such as the layered sodiumsilicates described in U.S. Pat. No. 4,664,839, issued May 12, 1987 toH. P. Rieck, incorporated herein by reference. However, other silicatesmay also be useful such as for example magnesium silicate, which canserve as a crispening agent in granular formulations, as a stabilizingagent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates, including sodium carbonate and sesquicarbonate and mixturesthereof with ultra-fine calcium carbonate as disclosed in German PatentApplication No. 2,321,001 published on Nov. 15, 1973, the disclosure ofwhich is incorporated herein by reference.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z (zAlO.sub.2.sup.. ySiO.sub.2)

wherein M is sodium, potassium, ammonium or substituted ammonium, z isfrom about 0.5 to about 2; and y is 1; this material having a magnesiumion exchange capacity of at least about 50 milligram equivalents ofCaCO₃ hardness per gram of anhydrous aluminosilicate. Preferredalumino-silicates are zeolite builders which have the formula:

    Na.sub.z [(AlO.sub.2).sub.z (SiO.sub.2).sub.y ].sup.. xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264. Useful aluminosilicate ion exchange materials arecommercially available. These aluminosilicates can be crystalline oramorphous in structure and can be naturally-occurring aluminosilicatesor synthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal., issued Oct. 12, 1976, incorporated herein by reference. Preferredsynthetic crystalline aluminosilicate ion exchange materials usefulherein are available under the designations Zeolite A, Zeolite P (B),and Zeolite X. In an especially preferred embodiment, the crystallinealuminosilicate ion exchange material has the formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].sup.. xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Preferably, the aluminosilicate has aparticle size of about 0.1-10 microns in diameter.

Specific examples of polyphosphates are the alkali metaltripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodiumand potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta phosphate in which the degree ofpolymerization ranges from about 6 to about 21, and salts of phyticacid.

Examples of phosphonate builder salts are the water-soluble salts ofethane 1-hydroxy-1, 1-diphosphonate particularly the sodium andpotassium salts, the water-soluble salts of methylene diphosphonic acide.g. the trisodium and tripotassium salts and the water-soluble salts ofsubstituted methylene diphosphonic acids, such as the trisodium andtripotassium ethylidene, isopyropylidene benzylmethylidene and halomethylidene phosphonates. Phosphonate builder salts of theaforementioned types are disclosed in U.S. Pat. Nos. 3,159,581 and3,213,030 issued Dec. 1, 1964 and Oct. 19, 1965, to Diehl; U.S. Pat. No.3,422,021 issued Jan. 14, 1969, to Roy; and U.S. Pat. Nos. 3,400,148 and3,422,137 issued Sep. 3, 1968, and Jan. 14, 1969 to Quimby, saiddisclosures being incorporated herein by reference.

Polycarboxylate builder can generally be added to the composition inacid form, but can also be added in the form of a neutralized salt. Whenutilized in salt form, alkali metals, such as sodium, potassium, andlithium, or alkanolammonium salts are preferred. Included among thepolycarboxylate builders are a variety of categories of usefulmaterials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates. A number of etherpolycarboxylates have been disclosed for use as detergent builders.Examples of useful ether polycarboxylates include oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al., U.S. Pat. No. 3,635,830, issued Jan. 18, 1972, both ofwhich are incorporated herein by reference.

A specific type of ether polycarboxylates useful as builders in thepresent invention also include those having the general formula:

    CH(A)(COOX)--CH(COOX)--O--CH(COOX)--CH(COOX)(B)

wherein A is H or OH; B is H or --O--CH(COOX)--CH₂ (COOX); and X is H ora salt-forming cation. For example, if in the above general formula Aand B are both H, then the compound is oxydissuccinic acid and itswater-soluble salts. If A is OH and B is H, then the compound istartrate monosuccinic acid (TMS) and its water-soluble salts. If A is Hand B is --O--CH(COOX)CH₂ (COOX), then the compound is tartratedisuccinic acid (TDS) and its water-soluble salts. Mixtures of thesebuilders are especially preferred for use herein. Particularly preferredare mixtures of TMS and TDS in a weight ratio of TMS to TDS of fromabout 97:3 to about 20:80. These builders are disclosed in U.S. Pat. No.4,663,071, issued to Bush et al., on May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds,particularly alicyclic compounds, such as those described in U.S. Pat.Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all ofwhich are incorporated herein by reference.

Other useful detergency builders include the etherhydroxypolycarboxylates represented by the structure:

    HO--[C(R) (COOM)--C(R)(COOM)--O].sub.n --H

wherein M is hydrogen or a cation wherein the resultant salt iswater-soluble, preferably an alkali metal, ammonium or substitutedammonium cation, n is from about 2 to about 15 (preferably n is fromabout 2 to about 10, more preferably n averages from about 2 to about 4)and each R is the same or different and selected from hydrogen, C₁₋₄alkyl or C₁₋₄ substituted alkyl (preferably R is hydrogen).

Still other ether polycarboxylates include copolymers of maleicanhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.Organic polycarboxylate builders also include the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids. Examplesinclude the sodium, potassium, lithium, ammonium and substitutedammonium salts of ethylenediamine tetraacetic acid, and nitrilotriaceticacid. Also included are polycarboxylates such as mellitic acid, succinicacid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylicacid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations, but can also beused in granular compositions. Suitable salts include the metal saltssuch as sodium, lithium, and potassium salts, as well as ammonium andsubstituted ammonium salts.

Other carboxylate builders include the carboxylated carbohydratesdisclosed in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 28, 1973,incorporated herein by reference.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986,incorporated herein by reference. Useful succinic acid builders includethe C₅ -C₂₀ alkyl succinic acids and salts thereof. A particularlypreferred compound of this type is dodecenylsuccinic acid. Alkylsuccinic acids typically are of the general formula R--CH(COOH)CH₂(COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon,e.g., C₁₀ -C₂₀ alkyl or alkenyl, preferably C₁₂ -C₁₆ or wherein R may besubstituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, allas described in the above-mentioned patents.

The succinate builders are preferably used in the form of theirwater-soluble salts, including the sodium, potassium, ammonium andalkanolammonium salts. Specific examples of succinate builders include:laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986. Examples of useful builders also include sodium andpotassium carboxymethyloxymalonate, carboxymethyloxysuccinate,cis-cyclo-hexanehexacarboxylate, cis-cyclopentane-tetracarboxylate,water-soluble polyacrylates (these polyacrylates having molecularweights to above about 2,000 can also be effectively utilized asdispersants), and the copolymers of maleic anhydride with vinyl methylether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylatesdisclosed in U.S. Pat. No. 4,144,226, Crutchfield et al., issued Mar.13, 1979, incorporated herein by reference. These polyacetalcarboxylates can be prepared by bringing together, under polymerizationconditions, an ester of glyoxylic acid and a polymerization initiator.The resulting polyacetal carboxylate ester is then attached tochemically stable end groups to stabilize the polyacetal carboxylateagainst rapid depolymerization in alkaline solution, converted to thecorresponding salt, and added to a surfactant.

Polycarboxylate builders are also disclosed in U.S. Pat. No. 3,308,067,Diehl, issued Mar. 7, 1967, incorporated herein by reference. Suchmaterials include the water-soluble salts of homo- and copolymers ofaliphatic carboxylic acids such as maleic acid, iraconic acid,methylenemalonic acid, fumaric acid, aconitic acid, citraconic acid andmethylenemalonic acid.

Other organic builders known in the art can also be used. For example,monocarboxylic acids, and soluble salts thereof, having long chainhydrocarbyls can be utilized. These would include materials generallyreferred to as "soaps." Chain lengths of C₁₀ -C₂₀ are typicallyutilized. The hydrocarbyls can be saturated or unsaturated.

Enzymes

Detersive enzymes can be included in the detergent compositions of thepresent invention for a variety of reasons including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains, forexample, and prevention of refugee dye transfer. The enzymes to beincorporated include proteases, amylases, lipases, cellulases, andperoxidases, as well as mixtures thereof. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.However, their choice is governed by several factors such as pH-activityand/or stability optima, thermostability, stability versus activedetergents, builders and so on. In this respect bacterial or fungalenzymes are preferred, such as bacterial amylases and proteases, andfungal cellulases.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B.subtilis and B.licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name Esperase^(@). Thepreparation of this enzyme and analogous enzymes is described in Britishpatent specification. No. 1,243,784 of Novo. Proteolytic enzymessuitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames ALCALASE™ andSAVINASE™ by Novo Industries A/S (Denmark) and MAXATASE™ byInternational Bio-Synthetics, Inc. (The Netherlands).

Of interest in the category of proteolytic enzymes, especially forliquid detergent compositions, are enzymes referred to herein asProtease A and Protease B. Protease A and methods for its preparationare described in European Patent Application 130,756, published Jan. 9,1985, incorporated herein by reference. Protease B is a proteolyticenzyme which differs from Protease A in that it has a leucinesubstituted for tyrosine in position 217 in its amino acid sequence.Protease B is described in European Patent Application Serial No.87303761.8, filed Apr. 28, 1987, incorporated herein by reference.Methods for preparation of Protease B are also disclosed in EuropeanPatent Application 130,756, Bott et al., published Jan. 9, 1985,incorporated herein by reference.

Amylases include, for example, a-amylases obtained from a special strainof B.licheniforms, described in more detail in British patentspecification No. 1,296,839 (Novo), previously incorporated herein byreference. Amylolytic proteins include, for example RAPIDASE™,International Bio-Synthetics, Inc and TERMAMYL™, Novo Industries.

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al., issued Mar. 6, 1984, incorporated herein byreference, which discloses fungal cellulase produced from Humicolainsolens. Suitable cellulases are also disclosed in GB-A-2.075.028;GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800, and cellulases produced by a fungas ofBacillus N or a cellulase 212-producing fungas belonging to the genusAeromonas, and cellulase extracted from the hepatopancreas of a marinemollusc (Dolabella Auricula Solander).

Suitable lipass enzymes for detergent usage include those produced bymicro-organisms of the of the Pseudomonas groups, such as Pseudomonasstutzeri ATCC 19.154, as disclosed in British Patent 1,372,034,incorporated herein by reference. Suitable lipases include those whichshow a positive immunological cross-reaction with the antibody of thelipase produced by the microorganism Pseudomonas fluorescens IAM 1057.This lipass and a method for its purification have been described inJapanese Patent Application 53-20487, laid open on Feb. 24, 1978. Thislipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,under the trade name Lipase P "Amano," hereinafter referred to as"Amano-P." Such lipases should show a positive immunologicalcross-reaction with the Amano-P antibody, using the standard andwell-known immunodiffusion procedure according to Ouchterlony (Acta.Med. Scan., 133, pages 76-79 (1950)). These lipases, and a method fortheir immunological cross-reaction with Amano-P, are also described inU.S. Pat. No. 4,707,291, Thom et al., issued Nov. 17, 1987, incorporatedherein by reference. Typical examples thereof are the Amano-P lipase,the lipase ex Pseudomonas fragi FERM P 1339 (available under the tradename Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERMP 1338 (available under the trade name Amano-CES), lipases exChromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB3673, commercially available from Toyo Jozo Co., Tagata, Japan; andfurther Chromobacter viscosum lipases from U.S. Biochemical Corp.,U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonasgladioli. Peroxidase enzymes are used in combination with oxygensources, e.g., percarbonate, perbonate, persulfate, hydrogen peroxide,etc. They are used for "solution bleaching" i.e. to prevent transfer ofdyes of pigments removed from substrates during wash operations to othersubstrates in the wash solution. Perodidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application Wo 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S, incorporated herein byreference.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent granules is also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. (incorporated herein byreference). Enzymes are further disclosed in U.S. Pat. No. 4,101,457,Place et al., issued Jul. 18, 1978, and in U.S. Pat. No. 4,507,219,Hughes, issued Mar. 26, 1985, both incorporated herein by reference.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al., issued Apr. 14, 1981, also incorporated hereinby reference.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.5 mg to about 3 mg, ofactive enzyme per gram of the composition.

For granular detergents, the enzymes are preferably coated or prilledwith additives inert toward the enzymes to minimize dust formation andimprove storage stability. Techniques for accomplishing this are wellknown in the art. In liquid formulations, an enzyme stabilization systemis preferably utilized. Enzyme stabilization techniques for aqueousdetergent compositions are well known in the art. For example, onetechnique for enzyme stabilization in aqueous solutions involves the useof free calcium ions from sources such as calcium acetate, calciumformate, and calcium propionate. Calcium ions can be used in combinationwith short chain carboxylic acid salts, preferably formates. See, forexample, U.S. Pat. No. 4,318,818, Letton et al., issued Mar. 9, 1982,incorporated herein by reference. It has also been proposed to usepolyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers,mixtures of polyvalent alcohols with polyfunctional apiphatic amines 9e.g., alkanolamines such as diethanolamine, triethanolamine,di-isopropanolamine, etc.), and boric acid or alkali metal borate.Enzyme stabilization techniques are additionally disclosed andexemplified in U.S. Pat. No. 4,261,868, issued Apr. 14, 1981 to Horn, etal., U.S. Pat. No. 3,600,319, issued Aug. 17, 1971 to Gedge, et al.,both incorporated herein by reference, and European Patent ApplicationPublication No. 0 199 405, Application No. 86200586.5, published Oct.29, 1986, Venegas. Non-boric acid and borate stabilizers are preferred.Enzyme stabilization systems are also described, for example, in U.S.Pat. Nos. 4,261,868, 3,600,319 and 3,519,570.

Bleaching Compounds--Bleaching Agents and Bleach Activators

The detergent compositions of the present invention may containbleaching agents or bleaching compositions containing bleaching agentand one or more bleach activators. When included, present bleachingcompounds will typically comprise from about 1% to about 20%, moretypically from about 1% to about 10%, of such detergent composition. Ingeneral, bleaching compounds are optional components in non-liquidformulations, e.g., granular detergents. If present, the amount ofbleach activators will typically be from about 0.1% to about 60%, moretypically from about 0.5% to about 40% of the bleaching compositions.The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents. Forwash conditions below about 50° C., especially below 40° C., it ispreferred that the compositions hereof not contain borate or materialwhich can form borate in situ (i.e. borate-forming material) underdetergent storage or wash conditions. Thus it is preferred under theseconditions that a non-borate, non-borate forming bleaching agent isused. Preferably, detergents to be used at these temperatures aresubstantially free of borate and borate-forming material. As usedherein, "substantially free of borate and borate-forming material" shallmean that the composition contains not more than about 2% by weight ofborate-containing and borate-forming material of any type, preferably,no more than 1%, more preferably 0%.

One category of bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof, suitable examplesof this class of agents include magnesium monoperoxy-phthalatehexahydrate, the magnesium salt of metachloroperbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecandeioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman,issued Nov. 20, 1984, U.S. patent application Ser. No. 740,446, Burns etal., filed Jun. 3, 1985, European Patent Application 0,133,354, Banks etal., published Feb. 20, 1985, and U.S. Pat. No. 4,412,934, Chung et al.,issued Nov. 1, 1983, all of which are incorporated by reference herein.Highly preferred bleaching agents also include6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No.4,634,551, issued Jan. 6, 1987 to Burns, et al., incorporated herein byreference.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate, sodiumpyrophosate peroxyhydrate, urea peroxyhydrate, sodium peroxide, andsubject perbonate monohydrate and tetrahydrate.

Peroxygen bleaching agents are preferably combined with bleachactivators, which lead to the in situ production in aqueous solution(i.e., during the washing process) of the peroxy acid corresponding tothe bleach activator.

A wide range of bleach activators can be used, examples being disclosedin Spadini et al U.S. Pat. No. 4179390. Preferred bleach activatorsinclude tetraacetyl alkylene diamines, particularly tetraacetyl ethylenediamine (TAED) and tetraacetyl (TAGU). ##STR7## wherein R is an alkylgroup containing from about 1 to 18 carbon atoms wherein the longestlinear alkyl chain extending from and including the carbonyl carboncontains from about 6 to about 10 carbon atoms and L is a leaving group,the conjugate acid of which has a pK_(a) in the range of from 4 to about13. These bleach activators are described in U.S. Pat. No. 4,915,854,issued Apr. 10, 1990 to Mao, et al., incorporated herein by reference,and U.S. Pat. No. 4,412,934, which was previously incorporated herein byreference. Bleaching agents other than oxygen bleaching agents are alsoknown in the art and can be utilized herein. One type of non-oxygenbleaching agent of particular interest includes photo-activatedbleaching agents such as sulfonated zinc and/or aluminumphthalocyanines. These materials can be deposited upon the substrateduring the washing process. Upon irradiation with light, in the presenceof oxygen, such as by hanging clothes out to dry in the daylight, thesulfonated zinc phthalocyanine is activated and, consequently, thesubstrate is bleached. Preferred zinc phthalocyanine and aphotoactivated bleaching process are described in U.S. Pat. No.4,033,718, issued Jul. 5, 1977 to Holcombe et al., incorporated hereinby reference. Typically, detergent compositions will contain about0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.

Polymeric Soil Release Agent

Any polmeric soil release agents known to those skilled in the art canbe employed in the detergent compositions of the present invention.Polymeric soil release agents are characterized by having bothhydrophilic segments, to hydrophilize the surface of hydrophobic fibers,such as polyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion ofwashing and rinsing cycles and, thus, serve as an anchor for thehydrophilic segments. This can enable stains occurring subsequent totreatment with the soil release agent to be more easily cleaned in laterwashing procedures.

Polymeric soil release agents include cellulosic derivatives such ashydroxyether cellulosic polymers, copolymeric blocks of ethyleneterephthalate or propylene terephthalate with polyethylene oxide orpolyrropylene oxide terephthalate, and the like. Cellulosic derivativesthat are functional as soil release agents are commerically availableand include hydroxyethers of cellulose such as Methocel® (Dow).Cellulosic soil release agents also include those selected from thegroup consisting of C₁ -C₄ alkyl and C₄ hydroxyalkyl cellulose such asmethylcellulose, ethylcellulose, hydroxypropyl methycellulose, andhydroxybutyl methylcellulose. A variety of cellulose derivatives usefulas soil release polymers are disclosed in U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al., incorporated herein by reference.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g. C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. Such materialsare known in the art and are described in European Patent Application 0219 048, published Apr. 22, 1987 by Kud, et al. Suitable commerciallyavailable soil release agents of this kind include the Sokalan™ type ofmaterial, e.g., Sokalan™ HP-22, available from BASF (West Germany). Onetype of preferred soil release agent is a copolymer having random blocksof ethylene terephthalate and polyethylene oxide (PEO) terephthalate.More specifically, these polymers are comprised of repeating units ofethylene terephthalate and PEO terephthalate in a mole ratio of ethyleneterephthalate units to PEO terephthalate units of from about 25:75 toabout 35:65, said PEO terephthalate units containing polyethylene oxidehaving molecular weights of from about 300 to about 2000. The molecularweight of this polymeric soil release agent is in the range of fromabout 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays,issued May 25, 1976, which is incorporated by reference. See also U.S.Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 (incorporated byreference) which discloses similar copolymers. Another preferredpolymeric soil release agent is a polyester with repeat units ofethylene terephthalate units containing 10-15% by weight of ethyleneterephthalate units together with 90-80% by weight of polyoxyethlyeneterephthalate units, derived from a polyoxyethylene glycol of averagemolecular weight 300-5,000, and the mole ratio of ethylene terephthalateunits to polyoxyethylene terephthalate units in the polymeric compoundis between 2:1 and 6:1. Examples of this polymer include thecommercially available material Zelcon® 5126 (from Dupont) and Milease®T (from ICI). These polymers and methods of their preparation are morefully described in U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, toGosselink, which is incorporated herein. Other suitable polymeric soilrelease agents include the ethyl or methyl-capped 1,2-propyleneterephthalate-polyoxy- ethylene terephthalate polyesters of U.S. Pat.No. 4,711,730, issued Dec. 8, 1987, to Gosselink et al., the anionicend-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26,1988, to Gosselink, wherein the anionic end-caps comprisesulfo-polyethoxy groups derived from polyethylene glycol (PEG), theblock polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issuedOct. 27, 1987 to Gosselink, having polyethoxy endcaps of the formulaX--(OCH₂ CH₂)_(n) -- wherein n is from 12 to about 43 and X is a C₁ -C₄alkyl, or preferably methyl, all of these patents being incorporatedherein by reference.

Additional soil release polymers include soil release polymers of U.S.Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al., whichdiscloses anionic, especially sulfoaroyl, end-capped terephthalateesters, said patent being incorporated herein by reference. Theterephthalate esters contain unsymmetrically substitutedoxy-1,2-alkyleneoxy units. If utilized, soil release agents willgenerally comprise from about 0.01% to about 10.0%, by weight, of thedetergent compositions herein, typically from about 0.1% to about 5%,preferably from about 0.2% to about 3.0%.

Oct. 31, 1989 to Maldonado et al. All of these patents are incorporatedherein by reference. If utilized, soil release agents will generallycomprise from about 0.01% to about 10.0%, by weight, of the detergentcompositions herein, typically from about 0.1% to about 5%, preferablyfrom about 0.2% to about 3.0%.

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron and manganese chelating agents as a builder adjunct material.Such chelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures thereof, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents in compositionsof the invention can have one or more, preferably at least two, units ofthe substructure ##STR8## wherein M is hydrogen, alkali metal, ammoniumor substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3,preferably 1. Preferably, these amino carboxylates do not contain alkylor alkenyl groups with more than about 6 carbon atoms. Operable aminecarboxylates include ethylenediaminetetraacetates,N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethyl enetetraaminehexa-acetates,diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,ammonium, and substituted ammonium sales thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in thedetergent compositions of the invention when at lease low levels oftotal phosphorus are permitted in detergent compositions. Compounds withone or more, preferably at least two, units of the substructure ##STR9##wherein M is hydrogen, alkali metal, ammonium or substituted ammoniumand x is from 1 to about 3, preferably 1, are useful and includeethylenediaminetetrakis (methylenephosphonates), nitrilotris(methylenephosphonates) and diethylenetriaminepentakis(methylenephosphonates). Preferably, these amino phosphonates do notcontain alkyl or alkenyl groups with more than about 6 carbon atoms.Alkylene groups can be shared by substructures.

Polyfunctionally--substituted aromatic chelating agents are also usefulin the compositions herein. These materials can comprise compoundshaving general formula ##STR10## wherein at least one R is --SO₃ H or--COOH or soluble salts thereof and mixtures thereof. U.S. Pat. No.3,812,044, issued May 21, 1974, to Connor et al., incorporated herein byreference, discloses polyfunctionally--substituted aromatic chelatingand sequestering agents. Preferred compounds of this type in acid formare dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfo-benzene.Alkaline detergent compositions can contain these materials in the formof alkali metal, ammonium or substituted ammonium (e.g. mono-ortriethanol-amine) salts. If utilized, these chelating agents willgenerally comprise from about 0.1% to about 10% by weight of thedetergent compositions herein. More preferably chelating agents willcomprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents

Clay soil removal/anti-redeposition agents useful in the detergentcompositions of the present invention include polyethylene glycols andwater-soluble ethoxylated amines having clay soil removal andanti-redeposition properties, as well as additional polyamino compoundsderived from aspattic acid but not containing glutamic acid.

Polyethylene glycol compounds useful in the detergent compositions ofthe present invention typically have a molecular weight in the range offrom to about 1,000 to about 20,000, more preferably from about 2,000 toabout 12,000, most preferably from about 4,000 to about 8,000. Suchcompounds are commercially available and are sold as Carbowax^(@), whichis available from Union Carbide, located in Danbury, Conn. The watersoluble ethoxylated amines are preferably selected from the groupconsisting of:

(1) ethoxylated monamines having the formula:

    (X--L)--N--R(R.sup.2).sub.2

(2) ethoxylated diamines having the formula: ##STR11## (3) ethoxylatedpolyamines having the formula: ##STR12## (4) ethoxylated amine polymershaving the general formula: ##STR13## and (5) mixtures thereof; whereinA¹ is: ##STR14## or --O--; R is H or C₁ -C₄ alkyl or hydroxyalkyl R¹ isC₂ -C₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, ora C₂ -C₃ oxyalkylene moiety having from 2 to about 20 oxyalkylene unitsprovided that no O--N bonds are formed; each R² is C₁ -C₄ orhydroxyalkyl, the moiety --L--X, or two R² together form the moiety--(CH₂)_(r), --A² --(CH₂)_(s) --, wherein A² is --O-- or --CH₂ --, r is1 or 2, s is 1 or 2, and r+s is 3 or 4; X is a nonionic group, ananionic group or mixture thereof; R³ is a substituted C₃ -C₁₂ alkyl,hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites;R⁴ is C₁ -C₁₂ alkylene, hydroxyakylene, alkenylene, arylene oralkarylene, or a C₂ -C₃ oxyalkylene moiety having from 2 to about 20oxyalkylene units provided that no O--O or O--N bonds are formed; L is ahydrophilic chain which contains the polyoxyalkylene moiety --((R⁵O)_(m) (CH₂ CH₂ O)_(n))--, wherein R⁵ is C₃ -C₄ alkylene orhydroxyalkylene and m and n are numbers such that the moiety --CH₂ CH₂O)_(n) -- comprises at least about 50% by weight of said polyoxyalkylenemoiety; for said monamines, m is from 0 to about 3, and n is at leastabout 6 when R¹ is C₂ -C₃ alkylene, hydroxyalkylene, or alkenylene, andat least about 3 when R¹ is other than C₂ -C₃ alkylene, hydroyalkyleneor alkenylene; for said polyamines and amine polymers, m is from 0 toabout 10 and n is at least about 3; p is from 3 to 8; q is 1 or 0; t is1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x+y+z at least 2;and y+z is at least 2.

The most preferred soil release and anti-redeposition agent areethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986, incorporated herein by reference. Another group of preferred claysoil removal/anti-redeposition agents are the cationic compoundsdisclosed in European Patent Application 111,965, Oh and Gosselink,published Jun. 27, 1984, incorporated herein by reference. Other claysoil removal/anti-redeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985, all of which are incorporated herein byreference.

The most preferred soil release and anti-deposition agents areethoxylated tetraethylenepentamine and the polythylene glycols having amolecular weight in the range of from about 4,000 to about 8,000.

Granular detergent compositions which contain such compounds typicallycontain from about 0.01% to about 10.0% by weight of the clay removalagent.

Polymeric Dispersing Agent

Polymeric polycarboxylate dispersing agents can advantageously beutilized in the detergent compositions of the present invention. Thesematerials can aid in calcium and magnesium hardness control. In additionto acting as a builder adjunt analogously to the polycarboxylatedescribed above in the Builder description, it is believed, though it isnot intended to be limited by theory, that these higher molecular weightdispersing agents can further enhance overall detergent builderperformance by inhibiting crystal growth of inorganics, by particulatesoil peptization, and by antiredeposition, when used in combination withother builders including lower molecular weight polycarboxylates. Thepolycarboxylate materials which can be employed as the polymericpolycarboxylate dispersing agent are these polymers or copolymers whichcontain at least about 60% by weight of segments with the generalformula: ##STR15## wherein X, Y, and Z are each selected from the groupconsisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy andhydroxymethyl; a salt forming cation and n is from about 30 to about400. Preferably, X si hydrogen or hydroxy, Y is hydrogent or carboxy, Zis hydrogen and M is hydrogen, alkali metal, ammonia or substitutedammonium.

Polymeric polycarboxylate materials of this type can be prepared bypolymerizing or copolymerizing suitable unsaturated monomers, preferablyin their acid form. Unsaturated monomeric acids that can be polymerizedto form suitable polymeric polycarboxylates include acrylic acid, maleicacid (or maleic anhydride), fumaric acid, iraconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein of monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form ranges from about2,000 to 10,000, more preferably from about 4,000 to 7,000 and mostpreferably from about 4,000 to 5,000. Water soluble salts of suchacrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions have been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967. This patent is incorporated herein byreference.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing agent. Such materials include the watersoluble salts of copolymers of acrylic acid and maleic acid. The averagemolecular weight of such copolymers in the acid form ranges from about5,000 to 100,000, preferably from about 6,000 to 60,000, more preferablyfrom about 7,000 to 60,000. The ratio of acrylate to maleate segments insuch copolymers will generally range from about 30:1 to about 1:1, morepreferably from about 10:1 to 2:1. Water-soluble salts of such acrylicacid/maleic acid copolymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble acrylate/maleatecopolymers of this type are known materials which are described inEuropean Patent Application No. 66915, published Dec. 15, 1982, whichpublication is incorporated herein by reference.

Polyamino dispersant compounds derived from aspartic acid but notcontaining glutamic acid are useful as additional polyamino disperantcompounds in the detergent compositions of the invention. Such polyaminodispersant compounds suitable for inclusion herein are disclosed inEP-A-305282, EP-A-305283 and EP-A-351629.

If utilized, the polymeric dispersing agents will generally comprisefrom about 0.2% to about 10%, preferably form about 1% to about 5% byweight of the laundry detergent compositions.

Brightener

Optical brighteners or other brightening or whitening agents known tothose skilled in the art can be incorporated into the laundry detergentcompositions of the present invention. However, the choice of brightenerwill depend upon a number of factors, such as the type of detergent, thenature of other components present in the detergent composition, thetemperatures of wahs wash, the degree of agitation, and the ratio of thematerial washed to tub size.

The brightener selection is also dependent upon the type of material tobe cleaned, e.g. cottons, synthetics, etc. Since most laundry detergentproducts are used to clean a variety of fabrics, the detergentcompositions should contain a mixture of brighteners which will beeffective for a variety of fabrics. It is of course necessary that theindividual components of such a brightener mixture be compatible.

Commercial optical brighteners can be classified into subgroups whichinclude, but are not necessarily limited to, derivatives of stilbene,pyrazoline, coumarin, carboxylic acid, methine cyanines,dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Examples of suchbrighteners are disclosed in "The Production and Application ofFluorescent Brightening Agents", M. Zahradnik, Published Dy John Wiley &Sons, New York (1982), the disclosure of which is incorporated herein byreference.

Stilbene derivatives include, but are not necessarily limited to,derivatives of stilbene; triazole derivatives of stilbene; oxadiazolederivatives of stilbene; oxazole derivatives of stilbene; and stryl ofstilbene.

Certain derivatives of bis(triazinly) aminostilbene may be prepared from4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives include, but are not necessarily limited to,derivatives substituted in the 3-position, in the 7-position, and in the3- and 7-positions. Carboxylic acid derivatives include, but are notnecessarily limited to, fumaric acid derivatives; benzoic acidderivatives; p-phenylene-bis-acrylic acid derivatives;naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives;and cinnamic acid derivatives.

Cinnamic acid derivatives can be further subclassified into groups whichinclude, but are not necessarily limited to, cinnamic acid derivatives,styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, andstyrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.

The styrylazoles can be further subclassified into styrylbenzoxazoles,styrylimidazoles and styrylthiazoles, as disclosed on page 78 of theZahradnik reference. It will be understood that these three identifiedsubclasses may not necessarily reflect an exhaustive list of subgroupsinto which styrylazoles may be subclassified.

Other optical brighteners are the derivatives ofdibenzothiophene-5,5-dioxide disclosed at page 741-749 of TheKirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages 737-750(John Wiley & Son, Inc., 1962), the disclosure of which is incorporatedherein by reference, and include 3,7-daiminodibenzothiophene-2,8-disulfonic acid5, 5 dioxide.

Other optical brighteners are azoles, which are derivatives of5-membered ring heterocycles. These can be further subcategorized intomonoazoles and bisazoles. Examples of monazoles and bisazoles aredisclosed in the Kirk-Othmer reference.

Examples of such compounds include brighteners derived from pyrazine andbrighteners derived from 4-aminonaphthalamide.

In addition to the brighteners already described, miscellaneous agentsmay also be useful as brighteners. Examples of such miscellaneous agentsare disclosed at pages 93-95 of the Zanradnik reference, and include1-hydroxy-3,6,8-pyrenetrisulfonic acid;2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene;4,5-diphenylimidazolonedisulfonic acid; and derivatives ofpyrazolinequinoline.

Other specific examples of optical brightener are those identified inU.S. Pat. No. 4,790,856, issued to Wixon on Dec. 13, 1988, thedisclosure of which is incorporated herein by reference. Thesebrighteners include the Phorwhite™ series of brighteners from Verona.Others brighteners disclosed in this reference include: Tinopal UNPA,Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CCand Artic White CWD, available from Hilton-Davis, located in Italy; the2-(4-styrylphenyl)-2H-naphthol(1,2-d)triazoles;4,4'-bis-(1,2,3-triazol-2-yl)-stilbene; 4,4'-bis(styryl)bisphenyls; andthe y-amino-coumarins. Specific examples of these brighteners include4-methyl-7-diethylamino coumarin; 1,2-bis(-bensimidazol-2-yl)-ethylene;1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)-thiophene;2-styryl-naphth-(1,2-d)-oxazole; and2-(stilbene-4-yl)-2H-naphtho(1,2d)triazole.

Still other optical brighteners include those disclosed in U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton, the disclosure of which isincorporated herein by reference.

If utilized, the optical brighteners will generally comprise from about0.05% to about 2.0%, preferably from about 0.1% to about 1.0% by weightof the laundry detergent compositions.

Suds Suppressors

Compounds known, or which become known, for reducing or suppressing theformation of suds can be incorporated into the detergent compositions ofthe present invention. The incorporation of such materials, hereafter"suds suppressor", can be desirable because the polyhydroxy fatty acidamide surfactants hereof can increase suds stability of the detergentcompositions. Suds suppression can be of particular importance when thedetergent compositions include a relatively high sudsing surfactant incombination with the polyhydroxy fatty acid amide surfactant.

Suds suppression is particularly desirable for compositions intended foruse in front loading automatic washing machines. These machines aretypically characterized by having drums, for containing the laundry andwash water, which have a horizontal axis and rotary action about theaxis. This type of agitation can result in high suds formation and,consequently, in reduced cleaning performance. The use of sudssuppressors can also be of particular importance under hot water washingconditions and under high surfactant concentration conditions.

A wide variety of materials may be used as suds suppressors. Sudssuppressors are well known to those skilled in the art. They aregenerally described, for example, in Kirk Othmer Encyclopedia ofChemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley& Sons, Inc., 1979). One category of suds suppressor of particularinterest encompasses monocarboxylic fatty acids and soluble saltsthereof. These materials are discussed in U.S. Pat. No. 2,954,347,issued Sep. 27, 1960 to Wayne St. John, said patent being incorporatedherein by reference. The monocarboxylic fatty acids, and salts thereof,for use as suds suppressors typically have hydrocarbyl chains of 10 toabout 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable saltsinclude alkali metal salts such as sodium, potassium, and lithium salts,and ammonium and alkanolammonium salts. These materials are a preferredcategory of suds suppressor for detergent compositions.

The detergent compositions of the present invention may also containnon-surfactant suds suppressors. These include, for example, highmolecular weight hydrocarbons such as paraffin, fatty acid esters (e.g.,fatty acid triglycerides), fatty acid esters of monovalent alcohols,aliphatic C₁₈ -C₄₀ ketones (e.g. stearone), etc. Other suds inhibitorsinclude N-alkylated amino triazines such as tri- to hexaalkylemlaminesor di- to tetra-alkyldiamine chlortriazines formed as products ofcyanuric chloride with two or three moles of a primary or secondaryamine containing 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., sodium, potassium, lithium) phosphates andphosphate esters. The hydrocarbons, such as paraffin and haloparaffin,can be utilized in liquid form. The liquid hydrocarbons will be liquidat room temperature and atmospheric pressure, and will have a pour pointin the range of about -40° C. and about 5° C., and a minimum boilingpoint not less than about 100° C. (atmospheric pressure). It is alsoknown to utilize waxy hydrocarbons, preferably having a melting pointbelow about 100° C. The hydrocarbons constitute a preferred category ofsuds suppressor for detergent compositions. Hydrocarbon suds suppressorsare described for example in U.S. Pat. No. 4,265,779, issued May 5, 1981to Gandolfo et al., incorporated herein by reference. The hydrocarbons,thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturatedor unsaturated hydrocarbons having from about 12 to about 70 carbonatoms. The term "parrafin" as used in this suds suppressor discussion,is intended to include mixtures of true paraffins and cyclichydrocarbons.

Another preferred category of non-surfactant suds comprises siliconesuds suppressors. This category includes the use of polyorganosiloxaneoils, such as polydimethysiloxane, dispersions or emulsions ofpolyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed of fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al., and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.,both incorporated herein by reference.

Other silicone suds suppressors are disclosed in U.S. Pat. No.3,455,839, which relates to compositions and processes for defoamingaqueous solutions by incorporating therein small amounts ofpolydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al., and in U.S. Pat. No.4,652,392, Baginski et al., issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) Polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1500 cs. at 25° C.;

(ii) From about 5 to about 50 parts per 100 parts by weight of:

(i) of siloxane resin composed of (CH₃)₃ SiO_(1/2) units of S_(i) O₂units in a ratio of from CH₃)₃ SiO_(1/2) units and to SiO₂ units of fromabout 0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of:

(i) of a solid silica gel:

Suds suppressors, when utilized, are present in a "suds suppressingamoung". By "suds suppressing amount" is meant that he formulator of thecomposition can select an amount of this suds controlling agent thatwill control the suds to the extent desired. The amount of suds controlwill vary with the detergent surfactant selected. For example, with highsudsing surfactants, relatively more of the suds controlling agent isused to achieve the desired suds control than with low foamingsurfactants.

The detergent compositions of the present invention will generallycomprise from 0% to about 5% of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, will bepresent typically in amounts up to about 5%, by weight, of the detergentcomposition. Preferably, from about 0.5% to about 3% of fattymonocarboxylate suds suppressor is utilized. Silicone suds suppressorsare typically utilized in amounts up to about 2.0%, by weight, of thedetergent composition, although higher amounts may be used. This upperlimit is practical in nature, due primarily to concern with keepingcosts minimized and effectiveness of lower amounts for effectivelycontrolling sudsing. Preferably from about 0.01% to about 1% of siliconesuds suppressor is used, more preferably from about 0.25% to about 0.5%.As used herein, these weight percentage values include any silica thatmay be utilized in combination with polyorganosiloxane, as well as anyadjunct materials that may be utilized. Monostearyl phosphates aregenerally utilized in amounts ranging from about 0.1% to about 2% byweight of the compositions.

Hydrocarbon suds suppressors are typically utilized in amounts rangingfrom about 0.01% to about 5.0%, although higher levels can be used.

Other Ingredients

A wide variety of other ingredients which can be included in thedetergent compositions of the present invention include other activeingredients, carriers, hydrotropes, processing aids, dyes or pigments,solvents for liquid formulations, etc.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and1,3-propanediol) can also be used. The detergent compositions of thepresent invention will preferably be formulated such that during use inaqueous cleaning operations, the wash water will have a pH of betweenabout 6.5 and about 11, preferably between about 7.5 and about 10.5.Liquid product formulations preferably have a pH between about 7.5 andabout 9.5, more preferably between about 7.5 and about 9.0. Techniquesfor controlling pH at recommended usage levels include the use ofbuffers, alkali, acids, etc., and are well known to those skilled in theart. In laundry use, the composition of the present invention will bedissolved or dispersed in an aqueous medium, typically tapy water, andthe fabric to be cleaned will be immersed in the resultant washingliquor, with agitation if appropriate. The compositions can be used forsoaking, for washing by hand or in automatic laundry washing machines.The concentration of actives in the said liquor, the temperature, thedegree of agitation and the duration of the immersion may be varied,depending upon the nature of the fabric and the amount of soiling.

In addition to their use as dispersants, the polymers of glutamic acidmay also be used as chelating agents, e.g. for ions of such metals ascopper; as soil-release agents (especially when carrying hydrophobicsubstituents); and as dye-transfer inhibitors. The use of the saidpolymers in combination with conventional dispersants includingdispersants derived from aspartic acid but not containing glutamic acid,is not precluded. The present invention is not illustrated in and by thefollowing examples.

EXAMPLE 1

A 150 ml conical flask was flame-dried in argon and provided with athermometer, magnetic stirrer, reflux condenser and argon blanket via aNoramg bubbler. The flask was than charged with 2.50 g f L-glutamic acid(from Messrs. BDH) and 100 ml of dried tetrahydrofuran (THF). Theresultant mixture was then heated to 65° C. and 2.46 g of disphogene(trichloromethycholoroformate, from Messrs Fluka), were then added overa period of 9 minutes. There was visual evidence of gas evolution duringthe addition. The resultant mixture was then held at 65° C. for 3 hours,during which time virtually all of the solid dissolved. After cooling,the mixture was gravity filtered under argon and the solid washed withTHF and dried in vacuo. The solid residue (0.08 g) was thought to becomposed largely of unreacted starting material. The resultant filtratewas rotary evaporated (at a maximum bath temperature of 40° C.), toleave a pale yellow oil (4.78 g). This was slurried in 19 ml ethylacetate whereupon a white solid crystallized. Then 60 ml of 40°-60° C.petroleum ether were added under argon over 15 minutes and the whitesolid was then gravity filtered under argon, washed with petroleum etherand dried in vacuo. This yielded 2.42 g (yield=82.3%) of theN-carboxyanhydride of L-glutamic acid, probably in the a form. A 250 mlconical flask provided with a magnetic stirrer and an argon blanket wascharged with 0.87 g of the N-carboxyanhydride of L-glutamic acid(prepared as described in the preceding paragraph), 174 ml of driedacetonitrile and 0.31 g of sodium methoxide (from Messrs. Aldrich). Themixture was stirred at room temperature (approx. 20° C.) for 24 hoursand then about 4 g of solid carbon dioxide were added (to destroy excessbase). After stirring for a further 30 minutes, the mixture was gravityfiltered under argon and the solid was washed with acetonitrile anddried in vacuo to yield 0.84 g of poly(1-glutamic acid) in the form of ahygroscipic, glassy white solid.

EXAMPLE 2

A standard granular laundry detergent composition was prepared asfollows, where the components are given on a percentage weight basis.

    ______________________________________                                        LAS                   7.71                                                    TAS                   2.43                                                    TAE11                 1.10                                                    25E3                  3.26                                                    ZEOLITE A             19.5                                                    CITRATE               6.5                                                     CARBONATE             11.14                                                   PERBONATE             16.0                                                    TAED                  5.0                                                     DETPMP                0.38                                                    CMC                   0.48                                                    SUDS SUPPRESOR        0.5                                                     BRIGHTENER            0.24                                                    PHOTOACTIVATED BLEACH 0.002                                                   ENZYME                1.4                                                     SILICATE (2.0 RATIO)  4.38                                                    MGSO4                 0.43                                                    PERFUME               0.43                                                    SULPHATE              4.10                                                    ______________________________________                                    

Water and miscellaneous to balance

In the standard granular laundry detergent composition, the abbreviatedcomponent identifications have the following meanings:

    ______________________________________                                        LAS           Sodium linear C.sub.12 alkyl benezene                                         sulphonate                                                      TAS           Sodium tallow alkyl sulphate                                    TAE.sub.n     Tallow alcohol ethoxylated with n                                             moles of ethylene oxide per mole of                                           alcohol                                                         25EY          A C.sub.12-15 predominantly linear                                            primary alcohol condensed with an                                             average of Y moles of ethylene                                                oxide                                                           TAED          Tetraacetyl ethylene diamine                                    Silicate      Amorphous Sodium Silicate (SiO.sub.2                                          Na.sub.2 O ratio normally follows)                              Carbonate     Anhydrous sodium carbonate                                      CMC           Sodium carboxymethyl cellulose                                  Zeolite A     Hydrated Sodium Aluminosilicate                                               of formula Na.sub.12 (AlO.sub.2 SiO.sub.2 O                                   having a primary particle size in                                             the range from 1 to 10 micrometers                              Citrate       Tri-sodium citrate dehydrate.                                   Photoactivated                                                                              Tetra sulphonated Zinc                                          Bleach        phthalocyanine.                                                 Perbonate     Anhydrous sodium perbonate                                                    monohydrate bleach, empirical                                                 formula NaBO.sub.2.H.sub.2 O.sub.2.                             Enzyme        Mixed proteolytic and amylolytic                                              enzyme sold by Novo Industries AS.                              Brightener    Disodium 4,4'-bis(2-morpholino-4                                              anilino-s-triazin-6-ylamino)                                                  stilbene-2:2'-disulphonate.                                     DETPMP        Diethylene-triamine penta                                                     (methylene phosphonic acid),                                                  marketed by Monsanto under the                                                Trade name Dequest 2060.                                        Suds          25% paraffin wax Mpt 50° C., 17%                         Suppressor    hydrophobic silica, 58% paraffin                                              oil.                                                            Sulphate      Anhydrous sodium sulphate                                       ______________________________________                                    

A test composition according to the present invention was prepared byadding poly(L-glutamic acid), prepared according to the method ofExample 1, to the standard, granular laundry detergent composition asdescribed above, containing both nonionic and anionic surfactants butcontaining no polycarboxylate soil suspending agent. The poly(L-glumatic acid) was added in an amount of 4.25% by weight of thestandard composition. A comparison composition was provided by astandard, granular laundry detergent composition containing 4.25% byweight of a conventional polycarboxylatesoil-suspending/anti-redeposition agent, comprising a copolymer of 1:4,maleic/acrylic acid with an average molecular weight of about 80,000.

Stained cotton tea towels were prepared by taking a cotton tea towel andpainting on a set of tea stain. Stained polycotton test swatches werealso prepared by painting stains on to 10 cm * 10 cm samples ofpolycotton fabric.

The stained polycotton test swatches and cotton tea towels were washedat 60° C. in water of 25° hardness (Ca:Mg=3:1) in an AEG washing machinetogether with a ballast olad fo 2.5-3 kg of naturally soiled polycottonand polyester garments, using the aforesaid compositions. Tests werecarried out on the stains recorded below.

The effectiveness of the compositions in cleaning and stain removal werejudged by an expert panel of four judges, the results being recorded inpanel score units (psu) using the Scheffe scale, taking the resultsobtained using the comparison formulation as the standard (0.00) in eachtest. The results are given in the following table:

                  TABLE 1                                                         ______________________________________                                        Test          Composition with PGA                                            ______________________________________                                        Stain Removal:                                                                Enzymatic     0.29                                                            Greasy        0.72*                                                           Lipstick      0.69                                                            DMO           1.94*                                                           P. Greasy     0.25                                                            P. Make-up    0.56                                                            P. DMO        0.25                                                            Bleachable    0.39                                                            Clay 1        -1.06                                                           Clay 2        1.38*                                                           Clay 3        0.25                                                            Clay 4        0.00                                                            Clay 5        0.69                                                            Clay 6        0.38                                                            Clay 7        0.50                                                            ______________________________________                                         NOTES                                                                         *= result that was stasticially significant                                   p = polycoton test fabric                                                     PGA = Poly (Lglumatic acid)                                                   DMO = Dirty Motor oil                                                         Clays 1-7 = Different clays from a variety of U.K. and European sites.   

The above results show that the primary wash performance of thePGA-containing composition was at least comparable to that of the testformulation containing the conventionalsoil-suspending/anti-redesposition agent in the important area ofparticulate stain removal and provided the added benefit that the PGA ismore readily biodegradable than the conventional agent.

EXAMPLE 3

The effectiveness of a composition according to the present inventionwas tested by washing cotton cloth containing particulate stains (blackiron oxide) under ambient conditions in municipal water (12°-17° H.) for3 minutes in a washing machine. Four replicates were carried out and thewashed cloth was examined with a Hunter colour meter to give a total of16 readings per cloth, which were then averaged to provide an average Lvalue (L=95+ denotes whiteness, L=0 denotes black). The individual Lvalues were taken across the surface of the cloth.

The composition according to the present invention Was prepared byadding poly(L=glumatic acid) to a standard detergent formulation, asdescribed in Example 2. The formulation according to the presentinvention is designated (a) in the table of results hereinafter.Comparison tests were carried out using the above-described procedure(b) in the absence of any detergent formulation ofsoil-suspending/anti-redeposition agent, or in the presence of (c) astandard detergent formulation containing no polycarboxylatesoil-suspending/anti-redeposition agent, (d) the standard detergentformulation to which a conventional polycarboxylatesoil-suspending/anti-redeposition agent had been added at a level of4.25% by weight. The results are shown in the following table, whereinthe higher the value for L, the whiter the washed fabric.

                  TABLE 2                                                         ______________________________________                                               Formulation                                                                            L                                                             ______________________________________                                               (a)      65.8                                                                 (b)      51.6                                                                 (c)      56.6                                                                 (d)      57.7                                                                 (e)      70.4                                                          ______________________________________                                    

EXAMPLE 4

A test composition and a comparison composition were prepared asdescribed in Example 2. Naturally soiled wash loads of weight 2.5-3 kgwere washed at 60° C. in water of 24° H. in a washing machine usingthree compositions. Whiteness tracer fabrics (vest and terry cottonmaterial) were added to each load and single and multiple washings ofthe fabrics were carried out. The effectiveness of the compositions inwhiteness maintenance was judged by an expert panel of four judges, theresults being recorded in psu using the Scheffe scale, taking theresults obtained using the comparison formulation as the standard (0.00)in each test. The results are given in the following table:

                  TABLE 3                                                         ______________________________________                                        Whiteness    Composition with PGA                                             ______________________________________                                        Single cycle 0.44                                                             Four cycle   0.09                                                             ______________________________________                                    

The results indicate that the composition according to the presentinvention achieves at least parity in net performance with thecomparison composition.

EXAMPLE 5

Naturally soiled garments of total weight 2.5 to 3 kg were washed usingthe compositions and the washing conditions described in Example 2 andthe results were assessed in psu using the evaluation method describedin that example. The results are given in the following table:

                  TABLE 4                                                         ______________________________________                                        Soiled Garment  Composition Containing PGA                                    ______________________________________                                        Terry towelling 0.14                                                          Tea towelling   0.87                                                          Roller towelling                                                                              0.28                                                          Mixed cotton shirt material                                                                   0.79                                                          ______________________________________                                    

These results indicate that the composition of the present invention, inoverall cleaning performance, achieved at least parity with thecomparison composition.

It will of course be understood that the present invention has beendescribed above purely by way of example and that modifications ofdetail can be made within the scope of the invention.

What is claimed is:
 1. A cleaning composition comprising (a) from about0.1 to 15% by weight of a block copolymer comprising biodegradablepolyethylene glycol and poly (1-glutamic acid); and (b) a detersivesurfactant.
 2. A composition according to claim 1 wherein the detersivesurfactant component (b) is selected from the group consisting ofnonionic, anionic, cationic, ampholytic, and zwitterionic surfactants,and mixtures thereof.
 3. A composition according to claims 1 or 2incorporating from 0.2% to 10% by weight of additional polyaminodispersant compound, wherein the additional polyamino dispersantscompound is derived from aspartic acid and does not contain glutamicacid.